Beaeincr materials



l. L. MURRIE. PROCESS FOR CRACKING HYDROOARBON OILS DISTILLED FROM CRUDE PETROLEUM, SHALE OIL, AND OIL OBTAINED FROM GILSONITE OR SIMILAR HYDROCARBON BEARING MATERIALS, AND

APPARATUS THEREFOR. APPLICATION FILED AUG.2B, I922.

Patented Nov. 14, 1922.

U5 news-sum I.

gvwwnto'o JOHN L- MURRIE J. L. MURRIE. EROCESS F R CRACKING HYDROCAR'JON OILS DISTILLED mom CRUDE PETROLEUM, SHALE OIL, AND 0|; banmwmom susomrs on smum HYDROCAREGN BEARING MATERIALS; AND

' APPARATUS THEREFOR.

APPLICATlOPf FILED AUG.28, 1922.

\ Y #NN JOHN L. MURRIE;

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UNlTED STATES PATENT OFFlClE.

JOHN L. 'MURRIE, 0F YONKEBS, NEW YORK.

PROCESS FOR CRACKING HYDROCAREQN OILS DISTILLED FROM CRUDE PETROLEUM,

SHALE OIL, AND OIL OBTAINED FROIvI GILSONITE OR SIMILAR HYDROCAEIBON- BEARING- MATEHIALS, AND APPARATUS THEREFOR.

Original application filed May 12, 1920, Serial No. 380,719. Divided and this application filed August 28.

' 1922. Serial No. 584,679.

To all Whom it may concern:

Be it known that l, JoirN LlVlounm, a citizen. oi the United States, and a resident of the city of .if'onkers, county of lVestchestor, and State of New York, have invented a new and improved process for cracking hydrocarbon oils distilled from crude petroleum, shale oil, and oil obtained from gilsonite or similar hydrocarbon-bearing materials, and apparatus therefor, of which the following is a specification, reference being had to the accompanying drawings.

This application is a division of an application filed by me May 12, 1920., Serial Numher 380,719.

Generally stated, the objects of my invention are to provide means "for rcn'ioving the carbon and other impurities from the cracked oil" to regulate the pressure in the etort, to expedite the cracking operations, to increase the quantity of the desired produrtru to maintain uniformity ot'tonuveratures in the bath and in the retort, tosimplity and reduce the cost of repairs and to reduce the generation of tired gases and the -tormation of unsaturated compounds.

My process and apparatus are adapted for deconrposing hydrocarbon oils, distillate and l'icavy petroleums by mixing them with a ed lrymlrocarbon gas and passing the mix; ture through a molten metal bath in order to produce an increased yield. oil? motor spirits or other low boiling point, high gravity liquids, and by the practice ot my process the reduction of heavy oils to light oils is very greatly expedited and the quality and quantity of the resulting products improved. and increased.

Although my process and apparatus are peculiarly adapted to the treatment of l'lcavy oils for the extraction therefrom-ct the various well known lighter compounds. yet will be understood that during the operation the tenuierature, the pressure. the ate oi lion of oil, etc., should be regulated acrorilingr to the character ol the oil l sine; cracked in order to yield the desired results, these changes being made as occasion may require The processes heretofore ein 'wloyed in the or ring of oils by passing the oil through molten metal bath n a closed retort, result in the accumulation of deposits of carbon,

which reduce the ell'iciency ol the process and are dilticult to remove from the retort, and in most cases require that the operation of the retort be interrupted for aperiod to enable the operator to remove them.

In the practice of my invention the 11llX- ture of gas, oil and vapors rising rapidly through the molten metal bath keep it vigorously agitated and prevent accumulation of carbon within ithat'portion of the retort filled with molten metal. As the particles of carbon "formed in the metal bath rise to the surface thereof they are there held in suspension in a layer of oil made up oi": the condensed heavy fractions which flow back from the vapor line, the heavy fractions condensed on the Walls of that portion of the retort above the furnace and the unvaporized heavy hydrocarbons rising through the metal bath. The layer of oil with the carbon in suspension flows continuously and. of course automatically from the retort through a device, hereinafter described, which forms partof this invention and which I call the depth adjusting overflow header, to the car-- bon sr-ittling tank, thereby making my process arontinuous one, because it is not necessary to interrupt its operation in order to re more the carbon. The depth adjusting overfiow header is provided with a number of valve controlled openings at dill'ercnt elevations, whereby the operator is able to main tain the pret'erred depth of the layer of oil in orduto remove the carbon particles rising to the surface of the molten metal.

Likewise those processes heretofore employing a molten metal bath have been imperfect in their operation on account of the 1msatislacrory temperature regulation. This dilliculty is largely due to the practice of injecting the oils into a umltcn metal bath contained within a vertical tube or its equivalent. Upon the oil being injected into the bottom of such tube it imn'iediately breaks into vapors, which rapidly expanding expel a. large portion. of the mo ten metal from the tube. and there hein no body l" metal of the desired temperature Lmmediately at hand to replace that which has been thusexpelled, the somewhat cooled metal drops back into the tube and must be again brought up to the required temperature Therefore, in processes where tubes or the like are used,

the rate of cracking of the oil is relatively slow as rapid injection of the oil into the metal bath under these conditions will additionally reduce its temperature so that a point is soon reached where only a very small portion oi the oil is crzuzked, and consequently a small yield only of the desired products produced.

l. iind that my new construction, which embodies a melting pot as hereinafter described, is superior to the tube form, as a plurality 01 oil injection pipes may be used to conduct the oil to the pot without expelling: the molten metal th ereiirom by the expansion of the vapors because the molten metal is not confined in the imu'iediate vicinity of the points at which the oil is injected; therefore molten metal of the desired and. practically uniform temperature can freely circulate "throughout the entireinterior of the melting pot, because oi. the absence of impeding piping or other obstructions. My construction is also superior to the tube form in that as the melting pot is preferably wider at the top than at the bottom, more room is thereby provided for the expansion of the vapors in the metal bath, thus'causing a greater degree of cracking and less violent agitation of the molten metal.

Another importantieature of my construction is the location of the oil inlet and thermometer pipes upon the outside of the retort and near the bottom of the melting pot, whereby I obviate the di'iliculty encountered in operating certain cracking apparatus in which the oil injection and thermometer pipes descend through the top of the retort into the molten metal bath, in which construction great diiliculty is experienced in maintaining tight joints because these joints are subjected to high temperatures and are also in the vapor zone, and furthermore, it extremely difficult and dangerous to remove the top or cover section of the retort to which the vertical oil pipesare attached, as they are of necessity immersed in the molten metal bath which adheres firmly to the pipes when cooled.

Under my invention all. the before-mentioned diliiculties are avoided; and it will be especially noted that since, as above stated, the oil and thermometer pipes enter the wall of the melting pot near its bottom, they form no obstruction to the free circulation of the molten metal within the retort, as do the vertical pipes used in said other types of app a. 'atus.

Under my improved process and ap paratus described and illustrated herein, I pass through the molten metal bath, which is preferably lead, within the melting pot of the retort a mixture of oil and natural gas, or other gas oil? the permanent hydrocarbon class. The gas in the presence'ot the oilreduces the vapor pressure of the oil,

permitting a much more rapid expansion of the oil into vapor in the melting pot or the cracking zone, and also presents the oil in a more finely divided state to the heating element for cracking. Also injecting the gas with the oil through the molten metal bath saturates the cracking zone and retort with preferably an excess of permanent hydrocarbon gases, thereby lessening the tendency to form fixed gases from the oil when it is cracked. Thus the generation of fixed gases from the oil is reduced and the oil is presented to the heating element in a more finely divided form for cracking, thereby increasing the yield of valuable products containing a small peij'centage only of un saturated hydrocarbon compounds.

My process may be nacticed and my ap- )arati.1s operated. under atmospheric pressure, or from atmospheric pressure up to approximately 125 pounds per square inch and at varying temperatures as the character or quality of the material being treated requires. The pressure in the cracking retort is determined and regulated to obtain the maximum yield of light hydrocarbon products with the smallest amount of unsaturated hydrocarbon compounds from the heavy hydrocarbon oils.

Referring to the drawings, which illustrate apparatus adapted for use in practicing my process, Figure 1 is a longitudinal View, partly in vertical section, of the complete apparatus; Figure 2 is a vertical sectional view of the furnace and cracking retort taken at right angles to Fig. 1.; Figures 8, 4t and 5 are vertical sectional views of three modified forms of pipe for injecting the heavy hydrocarbon oils and into the molten metal.

Referring to F 1 and 2, 1 represents a suitable pump whereby the heavy hydrocarbon oil or distillate to be cracked is drawn from a tank (not shown) and pumped under constant pressure through a pipeline 2 into a preheatcr 3, located where preferred, and heated preferably by the waste gases from a combustion furnace 4: under the cracking retort 8. The incoming heavy hydrocarbon oil after being preheated is mixed in the line leading {mm the preheater as shown, with the heavier fraction or trac tions condensed out of the vapors in aerial. condenser 5 and with the unoracked oil, which comes from the surface 01 the molten metal bath in the cracking retort 8.

For a more clear understanding ot the invention the orderly description of the procedure will be interrupted to give a description 01: the operation showing the method by which the heavier fraction or fractions from aerial condenser 5 and the uncracked oil from the surface of the molten metal in the cracking retort 8 are or may be, if desired, joined with the incoming preheated heavy bydrocarl'ion oil con'iing from the preheater The heavier fraction or fractions condensed out of the vapors in aerial'condenser 5 are pumped by pump 7 through line 6 into the line leading from the pre heater 3 and mixed with the incoming heavy hydrocarbon oil as shown. The uncracked oil from the cracking retort 8 comes from a layer 9 upon the surface of the molten metal bath 9, which layer holds the carbon particles in suspension, and flows automatically from the surface of the molten bath through openings 9 see Fig. 2, made at different elevations in the depth adjusting header 10, and controlled by suitable valves 10 into the draw-off pipe 10", which is provided with pressure regulating valve 11, water jacket 12, water inlet pipe 12 and water outlet pipe 12 for cooling the oil below the vaporization point, to the carbon settling tank 13, where the carbon precipitates as shown, and the uncracked oil free from carbon is drawn through the line l t and carbon strainer 15 by a suitable pump 16 and is discharged through line 6 into the line leading from the preheater 3, together with the heavy fractions condensed from the vapors in the aerial condenser 5, as shown. The openings 9 in the depth adjusting header 10 are made at different elevations as shown so that the depth of the layer of oil above the molten metal bath may be regulated by the appro priate manipulation of the said valves 10 through which the oil will automatically overflow when the valve at the selected level has been reached. Although I have illus trated the depth regulating device on one side of the apparatus only, obvious y, especially if the size or shape of the melting pot makes it desirable, there may be as many depth regulating devices as may be deemed necessary to effect the desired removal of the uncracked oil and heavy fractions holdring the carbon impurities in suspension, suitable piping therefrom being arranged to pass the overflow material through the carbon settling tank 13.

Having shown the sources of the oils which are introduced into the cinching re-- tort, T will now proceed with the orderly description of the proc-ss. The natural. or other permanent hydrocarbon is drawn from suitable receptacle, not shown, and pumped by a suitable pl'lnl'ji) l7 under con stant pressure through a pipe 18 into a mi ing chamber 19, where the gas mixed with the preheuted'heavy h Qocarbon oil from the preheater the condensed. heavy fraction or fractions from the aerial condenser 5i, and the uncracked and cleansed oil from the settling tank 13.

The mixture of heavy hydrocarlmiI oils and gas from the mixing chamber 19 passes into manifolds 20 and thence by pipes 21,

under constant pressure and regulation by suitable valves 21., into the n'ielting pot which may beneficially be made of cast or other steel welded or otherwise attached to the bottom of the cracking retort 8, and within which is contained the bath of molten metal 9.

In the particular embodiment of my apparatus herein illustrated two melting pots are shown for the same furnace in the bottom of the same retort. Obviously one or more than two may be provided for the same furnace and retort. The melting pots are illustrated in the form of troughs, preferably from five to ten feet in length, about two feet in depth and having an internal width of say four inches at the bottom and six inches at the top; but obviously the special siape and dimensions may be varied to suit the requirements of the plant. They may be oblong, square, round or other shape, so long as the horizontal dimensions of the surface of the bath are greater than its depth, and preferably, although not n cessarily, they should be wider at the top por tion than at the bottom portion, as stated above.

The portion of the pipes 21 which passes through the combustion chamber 4: is in sulated with suitable material 23, and the pipes may be spaced along the melting pot say from eight to twelve or more inches apart, and may be a single pipe as shown in. Fig. 3, or one pipe fitted inside of another as shown in Fig. l, or one pipe inside of another pipe with molten metal 1-2 between them, as shown. in llig. 5. 21 is the usual thermometer pipe, preferably insulated as by the material 23.

The melting pots 22 are heated by the combustion oi? suitable fuel, such as gas, coal or fuel oil, in the furnace i, the desired cracking temperature being maintained.

The heavy hydrocarbon oils from line 2, condensed heavy fractions from aerial. condenser 5, and cleansed oil from tank 13, and the natural or other permanent hydrocarbon gas, injected into the melting pots 22, ascend through the molten metal, the oil dccomposing or cracking and forming the light hydrocarbon compounds. The light and heavy hydrocarbon vapors and gases accumulate in the vapor space 24 above the molten metal bath 9, and leave the cracking retort 8 through a vapor pipe 25. l The par ticles of carbon and unvaporizcd portion of the oil rise to the surface of the bath and leave the retort through the depth adjusting header it) as heretofore described The vapor pipe is equipped with a suitable valve 526 for regulating the pressure in the cracking retort A. portion of the un cracked oil, which, as stated, removes the carbon from the surface of the molten metal bath, condenses in the vapor pipe 25 and with boiler tubes inside.

flows back into the retort, as is well understood. A portion of the light and heavy hydrocarbon vapors and which on er the aerial condenser 5 from the vapor pipe '25 is condensed by fractional cooling, in the example shown, into sir; fractions. The light hydrocarbon vapors and gases which are not condensed therein leave the aerial condenser by a vapor line 27 and enter awater-cooled condenser 28. One part of the six condensed fractions is a heavy hydrocarbon fraction and is pumped back to the cracking retort by pump 7 as heretofore described. The other part a li ht hydro carbon fraction suitable for d stilling for motor spirits and flows through a line 25) into a watercooled cooler 30 and thence when cooledthrough a line fillto the rundown tanks, not shown. i ate],- for the water-cooled cooler enters through a line 32 and leaves by a line 2-33, flowing counter current to th hydrocarbon fraction.

The aerial condenser 5 may be a steel shell It is preferably so constructed that the air flows through the tubes and leaves by the stack 84L. A damper 35 is installed in the stack for air control which regulates the amount of condensed fractions produced. The vapors and gases are on the outside of the tubes and the condensed fractions are separated by the baflles 36.

The cooled gas and condensed fractions resulting. from the condensation of the light hydrocarbon vapors and gases in the watercooled condenser 28 pass therefrom through a pipe 3 7 and the condensed fraeiions are trapped off through a line 3 t the rundown tanks, not shown. The non-condensable gases are carried oil through a pipe 38 and n be run to'an absorption plant or to a gas holder for such use as desired. The water for cooling the condenser 28 enters through a line 420 and leaves through a line .41, flowing counter current to the hot liquid and gases. The water-cooled. condenser and the water-cooled cooler may be of any suitable construction, but I prefer to use the tubular form as shown. The water inside of the tubes and. the hot gases or liquid on the outside thereof. 1

It will be noted that by my process I secure a series of very important and valu-- able results:

1. the use of the depth adjusting; oven flow header the depth of oil holding the carbon in suspension will automatically be regulated-as desired. This is a very necessary feature as l find that in cracking different kinds of oil, some of them produce more carbon than others and therefore a greater depth of oil is required to carry it away.

2. The herein described form of melting pot is of distinct advantage it permits more rapid cracking due to its provision for vapor expansion w thout expelling the molten metal from the cracking Zone.

the gas in the. .u'escnce of t-he oil reduces the vapor pressure of the oil, iermitting a more rapid expansion of the oil. into vapor in the cracking Zone and also presents the oil. in more finely divided state to the heating elements for cracking and it'urtheqmore the saturation of the entire cracking retort with fixed hydrocarbon tends to reduce the generation of fated gasfrom the oil and the formation of unsaturated compounds.

By operating the retort under pressures varying from atmospheric to approximately 1 one hundred and twenty five pounds the pressure and corresponding may be regulated to produce the maximum yield of hydrocarbon products with the smallest amount of unsaturated hydrocarbon compounds.

It will be obvious to those who are familiar with such matters that the details of mechanical construction of the several parts of the apparatus herein described and illustrated, the piping connections, valving, etc, may be (piite extensively modified without departing from the essentials of the inventioin either as to the apparatus or the proc ess, and I therefore do not limit myself to the mechanical details described and illustrated.

ll claim:

1. In the cracking of hydrocarbon oils temgerature the described process consisting in introducing the i'iiiaterial to he treated in conjunction with a permanent hydrocarbon gas into the lower part of molten metal bath in a retort, collecting the resulting vapors and gases in the upper part of the retort, conveybone which holds the carbon impurities in suspension.

2. In the cracking of hydrocarbon oils the described process consisting in introducing the materlal to be treated 1n conjunctioir with a permanent hydrocarbon gas into the lower part of a molten metal bath in a re tort, collecting the resulting vapors and gases in the upper part of the retort, conveying them away and condensing them, continuously supplying to and witlulrawing from the surface of the bath a layer of the heavy fractions and unmporized hydrocan hons which holds the carbon in'ipurities in suspension, and adjusting the thickness or depth of the layer as required.

3. In the cracking oi? hydrocarbon oils the described process consisting in passing the oil to be treated through a molten metal bath in a retort, collecting the resulting vapors and gases in the upper part of the retort, conveying them away and condensing them, continuously supplying to and witlulrawing from the surtace ol' the bath a layer of the heavy fractions and unvaporized hydrocarhens which holds the carbon impurities in suspension, and regulating the thickness or depth of the layer as required by adjusting the height of the overflow at the outlet end of the retort and separating the carbon.

l. 111 the cracking of hydrocarbon oils the described process consisting in inoorporatin g with the oil to be treated a percentage oi? fixed hydrocarbon gas adapted to finely divide the oil, causing the oil and gas to pass through a molten metal bath in a retort, continuously maintaining upon the surface of the bath a layer of heavy hydrocarbons, predetermining and assuring the preferred depth of said layer by adjusting the height of the outlet at the delivery end of the retort, collecting the resulting vapors and gases in the upper part of the retort, and conveying them away and condensing them.

5. In the cracking of hydrocarbon oils the described process consisting in introducing the materials to be treated into the lower part of a molten metal bath in a retort, collecting the resulting vapors and gases in the upper part of the retort, conveying them away from the retort through an upnuirdly extending duct, condensing the vapors, contii'mously supi ilying to and witlulrz'twing from the surface of the bath a layer ol' the heavy fractions and uuvaporized hydrocarlions, among them the condensate and bachflow from said duct which layer holds the carbon impurities in suspension, and regulating the thickness or depth of the layer as required by adjusting the height of the overflow at the outlet end of the retort.

6. In the cracking of hydrocarbon oils the described process consisting in introducing the material to be treated into the lower part of a molten metal bath in a retort, collecting the resulting vapors and gases in the upper part of the retort, conveying them away through an upwardly extending duct, regulating the pressure in the retort and duct, condensing the vapors, continuously supplying to and withdrawing from the surface of the bath a layer oil the heavy fractions and unvaporized. hydrocarbons,

condui among them the condensate and backflow from said duct, which layer holds the carbon impurities in suspension, and regulating the thickness or depth of the layer as required by adjustin the height oi the overflow at the outlet end of the retort.

7. In the cracking of hydrocarbon oils the described process consisting in passing th material to be treated through a molten metal bath in a retort, continuously supplying to and withdrawing from the surface of the bath a layer oi? unvaporized hydrocarbons which holds the carbon impurities in suspension, and regulating the thickness or depth of the layer by adjusting the height of the overflow at the outlet end of the retort.

8. In an apparatus of the class stated a retort, a melting pot having greater hori- Zontal surface dimensions than depth located in the bottom of the retort, means to heat the melting pot and the retort, conduits discharging through the wall or the melting pot near its bottom without going through the retort, means to inject the ma terial to be treated through said conduits into the melting pot, means whereby the vapor-s and gases may escape from the upper part of the retort, means to regulate the pressure in the retort and a condenser for the vapors.

9. In an apparatus oi the class stated a retort, a melting pot located in the bottom of the retort, means to heat the melting pot and the retort, a pipe for the conveyance oi: the material to be treated, another pipe for the conveyance of a permanent iydrocarbon gas, a mixing chamber in which the material to be treated and the hydrocarbon gas are combined, a pre-heating coil in the line conveying the material to be treated, conduits leading from the mixing ch amber and discl'iarging into the lower part oi the melting pot, and means to inject the material to be treated from the mixing chamber into the melting not through said 10. lo an apparatus oi the class stated retort, a melting pot located in the bottom of the retort, means to heat the melting pot and the retort, a mixing chamber, a pipe l'or conveying the material to be treated to the mixing chamber, another pipe for conveying a permanent hydrocarbon to the mixing chamber, conduits leading from the mixing chamber to the lower part of the melting pot, means to inject the material to be treated and gas through said conduits, means whereby the gases may escape from the upper part of the retort under pressure, a condenser adapted'to separate the heavy from the light "fractions, means to return the heavy fractions under pressure to the material to be treated prior to its introduction into the mixing chamber, means to continuously supply a layer of the heavy fractions and unvaporized hydrocarbons upon the top of the molten metal bath in the melting pot, means to predetermine and assure the preferred depth of said layer, means to automatically carry the layer away, means to cool the layer, means to precipitate its impurities, and means to convey the cleansed residue of heavy fractions and unvaporized hydrocarbons and discharge the same into the line which conveys the material to he treated.

11. In an apparatus of the class stated a melting pot, means to continuously supply to and Withdraw from the surface of the contents of the melting pot a layer of un-' the height of the overflow at the outlet end of the retort.

12. In an apparatus of the class stated a retort, a melting pot having greater horizontal surface dimensions than depth located in the bottom of the retort, means to heat the melting pot and the retort, conduits discharging through the wall of the melting pot near its bottom without going through the retort, means to inject the material to be treated through said conduits into the melting pot, means whereby the vapors and gases may escape from the upper part of the retort, means to regulate the pressure in the retort and a condenser for the vapors.

JOHN L. MUHIHE. 

